EP1481281B1 - Verfahren zur herstellung eines anisotropen kristallfilms auf einer spenderplatte - Google Patents

Verfahren zur herstellung eines anisotropen kristallfilms auf einer spenderplatte Download PDF

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Publication number
EP1481281B1
EP1481281B1 EP03737659.7A EP03737659A EP1481281B1 EP 1481281 B1 EP1481281 B1 EP 1481281B1 EP 03737659 A EP03737659 A EP 03737659A EP 1481281 B1 EP1481281 B1 EP 1481281B1
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EP
European Patent Office
Prior art keywords
film
crystal film
plate
anisotropic
donor plate
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EP03737659.7A
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French (fr)
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EP1481281A4 (de
EP1481281A2 (de
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Pavel I. Lazarev
Natalya A. Ovchinnikova
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Nitto Denko Corp
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Nitto Denko Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the invention pertains to the field of fabricating devices for various purposes, which utilize anisotropic films: polarizers, retarders, etc. Such devices are for example liquid crystal displays, various displays, and indicatory elements.
  • the invention may also be used in fabrication of materials and products for automotive industry, architecture, and applied art. Besides that, the invention may be used to obtain coatings with anisotropic conductivity, magnetic properties, heat transfer and other physical properties.
  • the invention pertains to the technology of transferring anisotropic films or their portions from the donor plate to the receptor plate, which in turn may represent an element of the structure in a device, as well as the technology of a fabricating the donor plate for the purpose of the above transfer.
  • optically anisotropic crystal films which are obtained from organic dyes via special fabrication operations and therefore feature high degree of anisotropy, thermal and light resistance [ Gvon et al., US 5,739,296 ].
  • the mentioned films have been widely used as polarizing coatings, for example in fabrication of liquid crystal displays [ Khan et al., US 6,399,166 ].
  • Technology of fabricating the above films is relatively simple; however it requires special equipment and precise compliance with the fabrication conditions in order to provide reproducibility of parameters of films.
  • indicatory and other devices which mainly represents assembly of already prefabricated parts, it is sometimes difficult to incorporate an additional fabrication process to produce films and parts based on the above films.
  • polarizing coatings with the desired configuration one may also use flexo-stenciling, relief or gravure printing to apply the polarizing coating with a patterned layer of water-soluble lacquer. After solidifying the lacquer the exposed polarizing coating is washed off with a suitable solvent (water or a mixture of water with and organic solvent).
  • a suitable solvent water or a mixture of water with and organic solvent.
  • this method also requires carrying out several additional fabrication operations (installation of an additional fabrication station), and implementation of this method may raise difficulties in selecting suitable chemical agents (suitable composition of the lacquer for polarizing coating, solvent to remove the protective lacquer, etc.).
  • 3M Company has developed technology which allows avoiding installation of special fabrication processes for producing polarizing films, obtained from organic dyes, with various configurations [ Staral et al., US 5,693,446 ].
  • This technology is based on using pre-fabricated polarizing films on a base, the so called donors.
  • This technology involves the known methods of mass transfer as a result of localized heating of the coating areas to be transferred [ Chou et al., US 5,506,189 ]. Heating may be implemented via thermal elements, laser radiation, etc. This method allows obtaining polarizing coating of an arbitrary shape with high resolution of the pattern.
  • Polarizing coating is obtained from lyotropic liquid crystal (LLC) dyes, molecules of which aggregate into supramolecular complexes. After application of LLC onto the substrate and inflicting the external shearing force supramolecular complexes become aligned in the direction of the influence. After the film dries (removal of the solvent), alignment of molecules is conserved, which constitutes polarizing qualities of such coatings. Disorientation of molecules resulting from the heating leads to degradation of optical characteristics of the coating.
  • LLC lyotropic liquid crystal
  • anisotropic crystal films [ Fennell, L., Lazarev, P., Ohmura, S., Paukshto, M. "Thin Crystal Film PolarizersTM, Asia Display/DW'01, Proceedings of The 21st International Display Research Conference in conjunction with The 8th International Display Workshops, Nagoya, Japan, October 16-19, 2001, p. 641-603 ; Nazarov, V., Ignatov, L., Kienskaya, K. "Electronic spectra of aqueous solutions and films made of liquid crystal ink for thin film polarizers” (2001).
  • the crystal films feature better optical characteristics and resistance to external impacts. Crystallization of the mentioned films happens in the process of drying a layer of aligned liquid crystal solution, applied in a certain way. Consequently, in order to obtain reproducible degree of anisotropy in the transferred film, operation of drying the film formed on the donor plate should be designed such that the process of removing the solvent will occur under conditions, which provide formation of the crystal structure of the film. Besides that, another necessary condition of realization of the herein invention is the fact that the transfer of the anisotropic crystal film obtained from LLC should be carried out via not heating, but rather direct global or localized pressure (possibly by an impulse) applied onto the donor plate.
  • the heating along with other methods of activation processing in this transfer process plays only a facilitating role.
  • the localized heating even though its duration could be short, as described in [ Staral et al., US 5,693,446 ], represents the main propellant of the transfer of the anisotropic film, and it may lead to infringement of the film's structure and consequently degrade optical parameters due to significant temperature difference at the edge of the heated area.
  • JP 20001 004822 A discloses the manufacture of a colour filter.
  • Preliminary activation i.e. preliminary influence onto the transferring areas of the film such as to weaken bonds between molecules or supramolecular complexes in the structure thereby providing the transfer of areas of the film from the donor plate to the receptor plate at significantly lower pressure. This does not result in degradation of anisotropy at the edge of the transferring areas; conversely, this has a "healing" effect on the borderline structure.
  • the other aspect of the activation processing of transferring areas of the film is the kind of processing, be it thermal, electro-magnetic, ionic, radiation, etc., which weakens the bonds of the transferring areas with the donor plate or an underlying layer.
  • anisotropy of the transferring areas of the film will also be preserved, while the borderline areas may indicate the "healing" effect.
  • the present invention provides a method of forming anisotropic crystal film on a receptor plate via transferring it from a donor plate, comprising:
  • the technical result of the disclosed invention is the conservation of the high degree of anisotropy and optical parameters of films after the transfer ⁇ possibility to form anisotropic coating on a surface of any configuration (including curved) and various degree of surface roughness; possibility of transferring various sizes and shapes of films; possibility to transfer multilayer coatings, which comprise anisotropic film, and multicolor patterns.
  • the founding aspects of the disclosed invention which distinguishes it from the closest analogue and which allows achieving the above mentioned technical result, is the use of anisotropic crystal film obtained from molecularly aligned organic material, in particular a dye, which forms a liquid crystal phase, as well as the achievement of transfer of the film or its portions as a result of application of pressure.
  • Anisotropic crystal film which represents an element of the donor plate, may be placed directly on the base.
  • the base is made out of glass having a polymer film applied to a surface thereof
  • Anisotropic crystal film may also be placed within the layers formed on the base.
  • the choice of the material of such layers will be determined on one hand by the technology of fabricating anisotropic film (homogeneity of the surface, hydrophilic property, etc.), and on the other hand by the choice of the method of activation and applying the pressure to transfer this film.
  • the activation process is preferably performed only on the areas of the anisotropic film that are due for transfer, while the pressure could be applied over the entire area of the donor plate and/or receptor plate.
  • the activation process could be either local, in the areas to be transferred, or global over the entire surface of the structure.
  • Application of pressure in the first case may be local or global, while in the second case - only local.
  • Material, thickness and other parameters of the base, as well as the material, thickness and other characteristics of all utilized layers of the structure will be the determining factors when choosing particular regimes of activation and application of pressure.
  • the base could be transparent and non-transparent, but it is preferred that it has smooth surface.
  • the base is usually from 1 to 200 ⁇ m thick, most often it is 10-50 ⁇ m.
  • Additional layers are usually incorporated into the structure of the donor plate to provide the optimum conditions for transferring selected areas of anisotropic crystal film onto the receptor plate.
  • a so-called reactive layer is usually formed directly on the base and/or directly under the anisotropic crystal film; this reactive layer undergoes the most amount of changes in the process of activation and thus plays an important role in the process of transferring portions of the film.
  • This layer may be made out of a material that is the most sensitive to the energy of the activation influence, as compared to all or some of the other layers in the structure. This could be, for example, photo activating material, capable to absorb light more than other layers in the structure during activation, and thus create areas of highec temperature in an area of anisotropic film to be transferred. Examples of such materials are dyes, which absorb ultraviolet infra red or visible ranges, corresponding to the wavelength of the activating light, metallic films, oxides of metals or other suitable absorbing materials.
  • light absorbing materials are organic and inorganic materials like soot, metals, metallic oxides, metal sulfides.
  • Suitable chemical elements are from the groups Ib IIb, IIIa, IVa, IVb, Va, Vb, VIa, VIb and VIII of the Periodic table, as well as alloys of these elements with the elements of Groups Ia, IIa, and IIIb, or their mixtures. Additionally, this could be metals Al, Bi, Sn, B or Zn and their alloys or alloys of these metals with elements of Groups Ia, IIa and IIIb of the Periodic table. Additionally, this could be metallic oxides and sulfides Al, Bi, Sn, B, Zn, Ti, Cr, Mo, W, Co, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zr and Te, and their mixtures.
  • At least one of these materials may be added to one or more layers of the donor plate (for example, the base, reactive layer, adhesion layer, anisotropic crystal film, protective film, etc.), or to the material of the receptor plate.
  • the donor plate for example, the base, reactive layer, adhesion layer, anisotropic crystal film, protective film, etc.
  • Thickness of the reactive layer is usually chosen with the range of 0.01-10 ⁇ m depending on the material and method of activation.
  • the matrix may be any of the known polymers capable of forming a film, such as thermo-reactive or thermo-plastic polymers including phenol resin, for example NOVOLAK (which is thermoplastic phenol- formaldehyde resin), polyvinyl acetate, polyvinyl chloride, polyacrylate, cellulose ethers and complex ethers, nitrocelluslose, polycarbonates, and mixtures of these materials.
  • phenol resin for example NOVOLAK (which is thermoplastic phenol- formaldehyde resin), polyvinyl acetate, polyvinyl chloride, polyacrylate, cellulose ethers and complex ethers, nitrocelluslose, polycarbonates, and mixtures of these materials.
  • NOVOLAK thermoplastic phenol- formaldehyde resin
  • polyvinyl acetate polyvinyl chloride
  • polyacrylate polyacrylate
  • cellulose ethers and complex ethers nitrocelluslose
  • polycarbonates and mixtures of these materials.
  • thermo-activating material i.e. material having certain characteristics, for example low melting point, mostly depending on the temperature, as compared to the other materials in the structure (i.e. material undergoing softening or melting in the temperature range of the activation process).
  • Reactive layer made out of such material when heated may soften creating areas with decreased adhesion of the crystal film to the base.
  • One of the layers of the donor plate may be a polymer resin, wax, or wax-like material.
  • Suitable polymer resins usually melt of soften in the range of 20 - 180°C; such resins include polyethyleneglycols, aromatic sulfoamide resins, acrylate resins, polyimide resins, polychlorvinyl and chlorinated resins of polychlorvinyl, vinyl chloride - copolymers of ascetic ether of vinyl alcohol, urea resins, melamine resins, polyolephine, or copolymers of the above materials.
  • Wax or wax-like material facilitates transferring the structure onto the surface of the receptor plate, such as paper.
  • Suitable wax-like materials have their melting or softening point in the range from 35 to 140°C, and comprise (the supreme fatty acid), ethanolmines such as stearic acid monoethanolamide, laural acid monoethanolamide, coconut oil, complex ethers supreme fatty acid, glycerin complex ethers supreme fatty acid like glycerin mono stearic acid of complex-ether; wax such as bee wax, paraffin, crystalline wax, synthetic wax, etc. and their mixtures. Since the above materials are hydrophobic, in order to create uniform anisotropic crystal film, an intermediate hydrophilic layer has to be created on the surface of the donor plate. This hydrophilic layer will be transferred onto the receptor plate together with the anisotropic film in the process of the transfer.
  • an adhesion layer providing bondage of the anisotropic film with the receptor plate in the process and/or after the transfer.
  • adhesion layer may be represented by a so-called "sticky tape”.
  • pressure sensitive film In the capacity of the adhesive layer one may use pressure sensitive film, or the mentioned film may be a separate element of the structure, as in the donor plate as well as in the receptor plate.
  • the pressure sensitive film could be made out of, for example, polyvinylbutyral (PVB) or polyvinyl furfural (PVF).
  • Reactive layer may also be formed on the receptor plate, however using it on the receptor plate is limited by the structure of the end product. In this case activation leads to increase of adhesion of the upper layer of the donor plate (or the anisotropic crystal film) to the receptor plate. If a layer of such material is not included in the structure of the end product, activation layer can not be formed on the receptor plate.
  • Material and design of the receptor plate may vary over a wide range depending on the donor plate and the transfer method.
  • Anisotropic crystal film may also be transferred onto a significantly rough receptor plate (with surface roughness up to 100 ⁇ m).
  • a protective layer is usually formed on the surface of the donor plate; this layer is made out of a suitable material, for example polyethylene or polyterephthalat.
  • the mentioned layer is usually used to protect the entire structure (surface layer) in transportation and storage.
  • the mentioned protective layer may be removed right before the creation of the areas of anisotropic crystal film on the receptor plate.
  • the mentioned protective film is a necessary component of the structure formed as result of the transfer, it may be preserved, thus the fabrication process will be shortened.
  • the optimum structure of the donor plate is a "sandwich" of several layers: the base, reactive layer, anisotropic crystal film, adhesive layer and/or pressure sensitive film, and finally the protective layer of film.
  • the structure of the donor plate is not limited by the above sequence and number of layers; it may also contain additional layers or some functional layers could be excluded from the structure. This is determined firstly by the purpose (structure) of the forming coating, the method of activation and transfer and utilized materials.
  • Activation may be performed on the entire structure considered above, or at least a portion of one of the layers in the structure or at least one layer in the structure, for example at least a part of the anisotropic crystal film, and/or at least a portion of the reactive film.
  • Regimes of the activation process are usually selected with the condition to preserve the degree of anisotropy of the transferring regions of the crystal film and to ensure the transfer of at least a part of the film from the donor plate to the receptor plate as a result of the application of pressure.
  • the activation application of pressure is performed from the side of the donor plate, and/or from the side of the receptor plate, on at least the regions of the film to be transferred.
  • the donor plate contains the base coated with at least one anisotropic crystal film made from at least one organic material, molecules or fragments of molecules of which have flat structure.
  • the film may be of any configuration. Thus, it may be a continuous film of any size and shape, up to the full size of the donor plate. However, it is possible to form or apply the anisotropic crystal film of any size, up to just the required configuration for the subsequent transfer.
  • Anisotropic crystal film is usually represented by a crystal film, material of which contains aromatic rings and has Bragg peak at 0.34 ⁇ 0.02nm (3.4 ⁇ 0.2 ⁇ ) along one of the axes of crystallization.
  • the mentioned film is usually obtained from liquid crystal of at least one organic material, which forms lyotropic liquid crystal phase, via application of the liquid crystal on the base using an external aligning influence and subsequent drying.
  • the material most commonly used in the capacity of the organic material for obtaining liquid crystal with subsequent formation of anisotropic coating is at least one organic dye, which structure contains at least one ionogenic group, which provides its solubility in polar solvents in order to form liquid crystal phase, and/or at least one non-ionogenic group, which provides its solubility in polar and non-polar solvents in order to form liquid crystal phase, and/or at least one anti-ion, all of which in the process of formation of the optically anisotropic film either remain in the structure of a molecules or not.
  • the organic dye In the capacity of the organic dye one usually uses at least one organic dye with the formula: ⁇ K ⁇ (M) n , where, K - the dye, chemical formula of which contains ionogenic group or groups, same or different, which provide(s) its solubility in polar solvents in order to form liquid crystal phase, M - anti-ion, n - the number of anti-ions in a molecule of the dye, which can be a fraction when a single anti-ion belongs to several molecules and in the case when n > 1 the anti-ions may be different.
  • K - the dye, chemical formula of which contains ionogenic group or groups, same or different, which provide(s) its solubility in polar solvents in order to form liquid crystal phase
  • M - anti-ion M - anti-ion
  • n - the number of anti-ions in a molecule of the dye, which can be a fraction when a single anti-ion belongs to several molecules and in the case when n > 1 the anti
  • the film is mostly formed by the multitude of supramolecular complexes of one or several organic materials, wherein the supramolecular complexes are aligned in a particular fashion in order to provide anisotropy of the film's properties, in particular polarization of light.
  • the film may consist of at least two regions (fragments), situated in a single plane, axes of polarization of which on the surface of the film (in the surface layer) are directed at an angle from 0 to 90° relative to each other.
  • the film may be a polarizing film, and/or a retarder, and/or alignment film, and/or protective film, and/or a film simultaneously functioning as at least two of the mentioned films, in at least a portion of the thickness of the film and/or in at least one region of the spectrum and/or on at least a portion of the surface of the film.
  • the donor plate may additionally contain a reactive layer, situated between the base and the film, and/or an adhesion, sticky or pressure sensitive layer, situated on the top of the film, and/or the protective layer, situated on the surface of the structure.
  • a reactive layer situated between the base and the film
  • an adhesion, sticky or pressure sensitive layer situated on the top of the film
  • the protective layer situated on the surface of the structure.
  • a light/thermo absorbing material may be added to the contents of the material of the base and/or the reactive layer, and/or the film and/or the adhesion layer.
  • the base of the donor plate is made out of glass having a polymer film applied to a surface thereof.
  • the donor plate may additionally contain at least one layer formed on the anisotropic crystal film for its protection, and/or at least one layer promoting adhesion to the receptor plate in the process of the transfer, and/or at least one layer formed under the anisotropic crystal film to preserve the necessary degree of anisotropy during the transfer, and/or to facilitate separation of local region of the film during the transfer due to the difference in the bond strength between the layer and the base of the donor plate and the film, and/or due to modification of the underlying regions of the layer during activation.
  • At least one modifying additive may be added to the contents of the anisotropic crystal film in order to aid the transfer of the desired regions of the film.
  • Such modifying additive may be glycerin, amount of which should not exceed 0.1 % wt. in the contents of the film
  • Regions of the film to be transferred onto the receptor plate or the entire film before being brought into contact with the receptor plate may be processed with ions of 2- and 3-valence metals in order to make them insoluble in water. Such processing intensifies the transfer process while preserving the high degree of anisotropy of the film.
  • Such materials are, for example, the following dyes:
  • the value of the refraction index for the majority of organic materials varies with in 1.3 - 2.5; absorption coefficient may vary in the range from 0.0 to 1.5.
  • Anisotropy of parameter n j determines the phase-shifting properties (retarding properties) of the film, while anisotropy of k j - polarizing properties.
  • optically anisotropic film is simultaneously a retarder and a polarizer.
  • the film in this spectral range represents just a retarder, at the same time, it may absorb light (be a polarizer) in the UV range of the spectrum.
  • the absorption bands may be in different spectral ranges: UV, visible and IR or simultaneously in several spectral ranges.
  • the film may feature polarizing and retarding properties in one region of the spectrum, while in other regions only retarding, which will determine the field of its application.
  • the glass plates of suitable size are fabricated first, the surfaces of which are then modified to change adhesion of the polymer film to be applied later.
  • the surface of the glass plates hydrophobic one may use dimehtyldichlorosilane, hexamethyldisilanizan, stearic acid and other agents. Selection of the hydrophobizator is determined mainly by the thin polymer film applied later, which should satisfy the following requirements: be optically transparent, hydrophilic, mechanically strong, smooth, and no thicker than 100nm (1000 ⁇ ).
  • films of celluloid obtained via the method of pouring solution of celluloid (for example 1% solution in amylacetate) over the surface of water, or films of PVA, polyvinyl alcohol, (for example 5% concentration), obtained via adsorption of aqueous solutions or centrifuging.
  • a colloid solution (liquid crystal) of dichroic dye is prepared and applied onto the surface of the polymer film via a known method to provide formation of the anisotropic crystal film.
  • the process of application of the liquid crystal solution layer is coupled with simultaneous alignment of the already existing supramolecular complexes under the influence of viscous forces onset in during the application when the liquid layer is stretched or one layer is shifted relative to the other.
  • the coating tool may change the direction of motion over the surface of the receptor plate. The speed of motion and the law of change of the direction of motion will determine the orientation of the supramolecular complexes in the liquid crystal.
  • Liquid crystal is the preordered state of the system, from which, in the process of alignment of the supramolecular complexes and subsequent removal of the solvent while following the required technological conditions, an anisotropic crystal film (crystal film) is formed.
  • Controlling the thickness of the layer is performed through the content of the solid phase in the applied solution and the thickness of the wet layer on the receptor plate.
  • Manufacturing parameter during formation of such layers is the concentration of solution, which is conveniently controlled in the process.
  • Degree of crystallinity of the layer may be controlled via roentgenogram or via optical methods. Crystalline structure of the film is ensured by the combination of the manufacturing regimes of application, aligning influence and drying. Optimum condition for crystallinity will be the Bragg peak at 0.3nm ⁇ 0.02 nm (3.4 ⁇ 0.2 ⁇ ) along one of the crystallographic axes of the obtained film. Crystal films with these parameters are obtained for subsequent application on to the receptor plate.
  • activation is performer with the use of oxygen plasma processing to increase its adhesion properties.
  • one uses flexible receptor which is glued to the obtained multilayer structure of the donor plate using optically transparent glues, for example polyether, silicon-organic, epoxy, etc., and a printing roller.
  • optically transparent glues for example polyether, silicon-organic, epoxy, etc.
  • splitting pressure separates the entire multilayer structure from the glass and thus the anisotropic film is transferred onto the flexible carrier.
  • Activation may be performed as via modification of the surface of the glass base to provide its hydrophobic properties, as well as additionally via modification of the surface of the polymer film, for example via processing it with oxygen plasma to enhance its adhesion properties.
  • the first stage is to form a continuous anisotropic film on a smooth flat surface of the technological plate.
  • This may be a flexible polymer film or at first a glass receptor from which the anisotropic film will later be transferred onto a flexible polymer film (this way of fabrication is used to increase the quality of fabricated anisotropic films).
  • the second stage is to transfer the anisotropic crystal film from the flexible polymer film onto the wording surface of the base or any kind of layer of the donor plate, which features a previously formed relief, made from a positive photoresist patterned by photolithography and representing the negative pattern of one color of the CPM.
  • the remaining is the desired pattern of the polarizer film of the first layer on the receptor plate, and the receptor is ready to form numerous polarizer elements of other colors.
  • the surfaces of the glass receptors are made hydrophobic by first washing them in the acid Karo and then applying 1% solution of chromolane in isopropanole. After drying the obtained hydrophobic layer, the surface of the receptor plate is coated with 1% polyvinyl alcohol during 1 hour at 110°, which is then dried for 1 hour at 140°. Furthermore, according to the method [see US 6,174,394 B1 the surface is coated with anisotropic crystal film from LLC phase of phthalocyanine.
  • the surface is coated with lacquer based on the polyacrylic resin, after which the flexible PET, polyethylene terephthalate, donor film is glued to the created structure with polyisobutilene glue using a rubber roller.
  • the polarizer film is transferred onto the flexible donor film.
  • the flexible PET donor film with the polarizer film of a dichroic dye obtained in such a way is subjected to oxygen plasma processing for 5 seconds and placed in a humid medium with relative humidity of 85%.
  • the working surface of the base or the structure, intended for forming the donor plate for subsequent fabrication of CPM is coated with a positive photoresist via centrifuging, dried, exposed, developed in a standard developer, rinsed in distilled water and dried in a jet of argon.
  • the mentioned operations lead to formation of a relief on the surface of the receptor plate, which represents the inverse of the desired pattern on the film.
  • the receptor is baked for 5 seconds in oxygen plasma and coated with 1% aqueous solution of PVA via centrifuging.
  • the previously prepared flexible donor film coated with the polarizer film ofphthalocyanine dye is roll-pressed to the receptor using a rubber roller.
  • the obtained "sandwich” is compressed with 100-150 Ig/cm 2 for 15 minutes.
  • the glue layer is melted and the PET donor film is removed in an oven at 120°C.
  • the working plate is washed sequentially in toluol and another solvent (usually based on toluol, acetone and etylacetate) to remove remainders of the glue and lacquer.
  • the working plate (future donor plate) is placed in ultra sound bath with dioxane for 2-3 minutes. Then it is held in the oven for 30 minutes at 120°C to bond PVC, and then placed in solution of BaCl 2 . ( ⁇ 30mSm) for 20 - 30 minutes.
  • the polarizer matrix is protected with a layer of PVA, which is applied via centrifuging from 1% aqueous solution and dried for 30 minutes at 120°C.
  • the pattern of the second color layer is formed via performing all operations from the coating of a photoresist to drying of the protective layer. Additionally, the dye benzopurpurine is selected as the polarizer film.
  • Regimes in the examples can be different However, regimes of the above manufacturing operations may be used not only in the process of fabricating the donor plate, but also directly in the process of forming anisotropic crystal film via transfer.
  • the above film is brought into contact with the receptor, the area to be transferred is activated via localized heating to temperature 45-55°C; most commonly the temperature is in the range 30-50, or 40-65 °C.
  • Metallic plate situated under the donor plate can provide localized heating and can provide the foundation for subsequent application of pressure. Heating may continue for 0.5 minute depending on the speed of temperature increase (gradient), under different conditions the heating time may be 0.2-1 min, 1-5 min, 0.5-10 min or other.
  • the regimes of activation and applicable pressure are chosen with the condition that the contrast at the constant transmission and/or birefringence coefficient of the anisotropic crystal film after the transfer change no more than by 10%.
  • the contact is a compressive device. Also, this may be a sliding cartridge and matrix print head, which performs localized influence in the selected areas of the receptor. Scanning is operated with computer. Printing is performed in the predetermined places. As a result, an image with the configuration of the optically anisotropic film with high resolution is formed on the transparent receptor. The degree of anisotropy in the transferred areas is no less than in the original films.
  • the pixel size corresponds to the standard dot
  • the receptor when transferring a film with a certain configuration only a part of the image is applied, then the receptor is rotated to a certain angle and another image is applied.
  • the result is a multilayer coating, wherein the direction of optical anisotropy varies.
  • the mentioned technology may be used to form circular polarizer, etc.
  • Heating the film with the laser from one side leads to thermal heating of the film, illuminating it with UV lamp on the other side results in photochemical activation (sensibilization) of the reactive layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Claims (19)

  1. Verfahren zur Bildung eines anisotropischen Kristallfilms (4) auf einer Rezeptorplatte durch seine Übertragung von einer Spenderplatte (1), welches Verfahren folgendes aufweist:
    Aktivieren mindestens eines zu übertragenden Teils der gesamten Spenderplatte (1), die den anistotropischen Kristallfilm (4) und eine Basis (2) aufweist, so dass eine Anhaftung zwischen mindestens zwei der Schichten auf der Spenderplatte (1) verringert wird;
    wobei der Aktivierungsgrad ausreichend sein sollte, um eine anschließende Übertragung des Films (4) bei Aufbringen von Druck bereitzustellen, aber nicht ausreichend, um die kristalline Struktur des zu übertragenden Kristallfilms (4) zu unterbrechen;
    wobei die Basis (2) eine Glasplatte mit einem Polymerfilm ist, der auf eine Oberfläche davon aufgetragen ist, und die Aktivierung über eine Modifikation der Oberfläche der Glasplatte zur Bereitstellung von hydrophoben Eigenschaften ausgeführt wird;
    nach der Aktivierung, Inkontaktbringen der Rezeptorplatte (9) mit der Spenderplatte (1), die mindestens einen anisotropischen Kristallfilm (4) aufweist; und
    anschließendes Aufbringen von Druck mindestens auf einen Teil der gesamten Spenderplatte (1), die den Kristallfilm (4) aufweist, der auf die Rezeptorplatte (9) übertragen werden soll, wobei die Höhe des Drucks ausreichend für die Übertragung von mindestens einem Teil des Films (4) von der Spenderplatte (1) zu der Rezeptorplatte (9) und nicht ausreichend für die Unterbrechung der kristallinen Struktur des zu übertragenden Kristallfilms (4) sein sollte.
  2. Verfahren nach Anspruch 1, wobei Systeme der Aktivierung und des anwendbaren Drucks gewählt werden, unter der Bedingung, dass sich der Kontrast bei der konstanten Übermittlung und/oder der Doppelbrechungskoeffizient des anisotropischen Kristallfilms (4) nach der Übertragung nicht mehr als um 10% verändern.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, wobei der anisotropische Kristallfilm (4) aus Flüssigkristall von mindestens einem organischen Material erhalten wird, das eine lyotrope Flüssigkristallphase bildet, durch Aufbringen des Flüssigkristalls auf die Basis (2) unter Verwendung einer externen Justiereinwirkung.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei die Aktivierung auf einen Teil der gesamten Spenderplatte (1) mit dem zu übertragenden Kristallfilm (4) angewandt wird, und der Druck auf die gesamte Oberfläche der Spenderplatte (1), die übertragen werden soll, aufgebracht wird.
  5. Verfahren nach einem der Ansprüche 1 bis 3, wobei die Aktivierung auf die gesamte Spenderplatte (1) angewandt wird und der Druck auf den Teil der gesamten Spenderplatte (1), der den zu übertragenden Kristallfilm (4) aufweist, aufgebracht wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei die Struktur des anisotropen Kristallfilms (4), die für die Übertragung vorgegeben ist, im Voraus während der Herstellung der Spenderplatte oder auf der bereits fertiggestellten Spenderplatte (1) gebildet wird, bevor sie mit der Rezeptorplatte (9) in Kontakt gebracht wird.
  7. Verfahren nach Anspruch 1, wobei der Kristallfilm (4) aus mindestens einem organischen Material gebildet ist, das Flüssigkristall bilden kann, und aus Molekülen oder Fragmenten von Molekülen, die eine flache Struktur aufweisen.
  8. Verfahren nach Anspruch 7, wobei das Material des anisotropischen Kristallfilms (10) aromatische Ringe aufweist und die Bragg-Peak bei 3,4±0,2 A entlang einer der optischen Achsen aufweist.
  9. Verfahren nach Anspruch 7 oder 8, wobei das organische Material mindestens einen organischen Farbstoff aufweist, dessen Strukturformel mindestens eine ionogene Gruppe aufweist.
  10. Verfahren nach Anspruch 9, wobei der organische Farbstoff mindestens einen organischen Farbstoff der folgenden Formel aufweist: {K} (M)n, wobei, K - der Farbstoff, dessen chemische Formel ionogene Gruppe oder Gruppen aufweist, gleich oder unterschiedlich, welche ihre Löslichkeit in polaren Lösungsmittel bereitstellt/bereitstellen, um eine Flüssigkristallphase zu bilden, M - Antiion, n - die Anzahl von Antiionen in einem Molekül des Farbstoffs, die einen Bruchteil ausmachen können, wenn ein einziges Antiion zu mehreren Molekülen gehört und in dem Fall, wenn n > 1, können die Antiionen unterschiedlich sein.
  11. Verfahren nach Anspruch 7, wobei der Kristallfilm (4) als Teil einer Gruppe fungiert, die einen Polarisator-Film, Retarder-Film, Ausrichtungsfilm, Schutzfilm oder einen Film aufweist, der gleichzeitig als eine beliebige Kombination von mindestens zwei der erwähnten Filmen fungiert.
  12. Verfahren nach einem der Ansprüche 7 bis 10, wobei der anisotropische Kristallfilm (4) aus mindestens zwei Fragmenten besteht, deren optische Achsen bei einem Winkel von zwischen 0 und 90° relativ zueinander gedreht sind.
  13. Verfahren nach einem der Ansprüche 7 bis 12, wobei ein Lichtabsorbiermittel zu dem Inhalt des Materials der Basis (2) und/oder des anisotropischen Kristallfilms (4) hinzugefügt wird.
  14. Verfahren nach einem der Ansprüche 7 bis 13, wobei die Basis eine flache oder konvexe oder konkave Form der Oberfläche aufweist.
  15. Verfahren nach einem der Ansprüche 7 bis 14, wobei mindestens ein modifizierender Zusatz, welcher die Übertragung separater Bereiche fördert, in dem Inhalt des anisotropischen Kristallfilms (4) enthalten ist.
  16. Verfahren nach Anspruch 15, wobei der modifizierende Zusatz Glyzerin ist, das zu dem Material des Kristallfilms (4) in der Menge von weniger als 0,1 Gew.-% hinzugefügt ist.
  17. Verfahren nach einem der Ansprüche 7 bis 16, wobei der anisotropische Kristallfilm (4) in Form von mindestens einem Bereich eines Bildes, das nötig für die anschließende Übertragung ist, aufgebracht wird.
  18. Verfahren nach Anspruch 7, wobie mindestens ein Teil des anisotropischen Kristallfilms (4) in Form von Bereichen aufgebracht ist, die sich in der Farbe unterscheiden.
  19. Verfahren nach Anspruch 7, wobei der anisotropische Kristallfilm (4) mit Ionen von 2- oder 3-Valenzmetallen zur Konversion in eine Wasserunlöslichkeitsphase verarbeitet wird.
EP03737659.7A 2002-02-06 2003-02-06 Verfahren zur herstellung eines anisotropen kristallfilms auf einer spenderplatte Expired - Lifetime EP1481281B1 (de)

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RU2002102943/28A RU2002102943A (ru) 2002-02-06 Способ формирования анизотропной кристаллической пленки на подложке путем переноса с пластины носителя, пластина носитель анизотропной кристаллической пленки и способ ее изготовления
RU2002102943 2002-02-06
PCT/US2003/003521 WO2003067312A2 (en) 2002-02-06 2003-02-06 Method of fabricating anisotropic crystal film on a receptor plate via transfer from the donor plate, the donor plate and the method of its fabrication

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AU2003216178A1 (en) 2003-09-02
CN1688396A (zh) 2005-10-26
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AU2003216178A8 (en) 2003-09-02
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